1. Field of the Invention
The present invention relates to an ink composition for ink jet recording, comprising a copper complex colorant, such as a copper complex dye or a copper phthalocyanine pigment.
2. Background Art
Ink jet recording is a printing method wherein droplets of an ink composition are ejected and deposited onto recording media, such as paper, to conduct printing. This method has a feature that images having high resolution and high quality can be printed at a high speed by means of relatively inexpensive apparatuses. Properties associated with reliability, such as freedom from the occurrence of precipitate, such as precipitate, in the ink composition, good recovery from nozzle clogging, and excellent storage stability, are required for an ink composition for ink jet recording.
In the case of ink compositions using dyes as the colorant, metal ions (such as calcium, magnesium, silicon, and iron ions) contained in the ink compositions are sometimes causative of the occurrence of precipitate or deteriorated recovery from clogging. For this reason, these metal ions should be kept in a certain amount or less. For example, how to remove calcium ions is described in Japanese Patent Laid-Open No. 5073/1993.
According to studies conducted by the present inventors, however, for ink compositions using copper complex dyes, the occurrence of precipitate in the ink compositions or poor recovery from clogging was observed even under conditions such that the metal ions were controlled in the certain amount or less.
On the other hand, in the case of ink compositions using non-water-soluble pigments as the colorant, the particle diameter of the pigments per se sometimes causes the occurrence of precipitate or deteriorated recovery from nozzle clogging. Therefore, the regulation of the particle diameter is important to pigment-based ink compositions. Even though the particle diameter of ingredients in the ink composition is regulated at the time of the preparation of the ink composition, precipitate or the like often occurs prior to use of the ink composition. According to studies conducted by the present inventors, the occurrence of precipitate was observed in ink compositions containing copper complex colorants, such as copper phthalocyanine pigments or dyes having a copper complex structure.
The present inventors have now found that the regulation of the concentration of free copper ions in ink compositions for ink jet recording, containing a copper complex colorant, such as a copper complex dye or a copper phthalocyanine pigment, can effectively prevent the occurrence of precipitate and, at the same time, can realize, on a high level, various properties required of ink compositions for ink jet recording. The present invention has been made based on such finding.
Accordingly, it is an object of the present invention to provide a precipitation-free ink composition for ink jet recording.
It is another object of the present invention to provide an ink composition for ink jet recording which can realize, on a high level, various properties required of ink compositions for ink jet recording.
According to one aspect of the present invention, there is provided an ink composition for ink jet recording, comprising a copper complex colorant, said ink composition having a free copper ion concentration of not more than 10 ppm.
The ink composition according to the present invention contains a copper complex colorant as a colorant. According to a preferred embodiment of the present invention, specific examples of copper complex colorants usable herein include copper complex dyes and copper phthalocyanine pigments.
Specific examples of copper complex dyes usable herein include: C.I. Direct Violet 47, 48, 90, and 91; C.I. Direct Blue 86, 87, 90, 98, 194, 195, 196, 199, 226, and 248; C.I. Direct Brown 95, 100, 112, 194, and 211; C.I. Direct Black 71, 105, 106, 107, 108, and 146; C.I. Acid Red 161; C.I. Acid orange 87, 88, and 122; C.I. Acid Red 194, 209, 211, 215, and 216; C.I. Acid Blue 151, 154, 167, 168, 170, 171, 184, 187, 199, 229, and 234; C.I. Acid Green 56, 57, 60, and 65; C.I. Acid Brown 231, 232, 294, and 296; C.I. Acid Black 58, 60, 62, 64, 107, 108, 112, 115, 118, 119, 121, 122, 131, 132, 139, 140, 155, and 156; C.I. Mordant Blue 58; C.I. Solvent Yellow 61 and 80; C.I. Solvent Orange 37, 40, and 44; C.I. Solvent Red 83, 84, and 121; C.I. Solvent Violet 21; C.I. Solvent Blue 55; C.I. Solvent Black 22 and 23; C.I. Reactive Red 6, 7, 27, 32, and 130; C.I. Reactive Violet 1, 2, 3, 4, and 5; C.I. Reactive Blue 3, 7, 9, 10, 13, 14, 15, 18, 20, 21, 25, 26, 38, 40, 41, 43, 52, 63, 71, 72, 77, 79, 80, 105, 113, 15 118, 120, 121, 122, 131, 140, 147, and 148; C.I. Reactive Brown 14, 18, and 19; C.I. Reactive Black 1, 8, 9, 13, 31, and 35; C.I. Reactive Green 5, 12, 14, and 15.
According to a preferred embodiment of the present invention, the copper phthalocyanine pigment is represented by the following formula: 
wherein X represents a chlorine or bromine atom or a hydrogen atom; and n is an integer of 14 to 16.
The copper phthalocyanine pigment is more preferably selected from the group consisting of C.I. Pigment Green 7 and 36 and C.I. Pigment Blue 15: x wherein x is an integer of 1 to 6 with C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 3, and C.I. Pigment Blue 15: 6 being preferred pigments.
The content of the copper complex colorant in the ink composition may be properly determined. The copper complex colorant, however, is preferably about 0.1 to 20% by weight, more preferably about 1 to 10% by weight. When the copper complex colorant is a copper complex dye, the content of the copper complex dye is preferably about 0.1 to 20% by weight, more preferably about 1 to 10% by weight. When the copper complex colorant is a copper phthalocyanine pigment, the content of the copper phthalocyanine pigment is preferably about 1 to 10% by weight, more preferably about 2 to 5% by weight.
According to the ink composition of the present invention, the free copper ion concentration is not more than 10 ppm, more preferably not more than 5 ppm. Methods usable for regulating the free copper ion concentration include a method wherein the degree of the purification of the colorant is enhanced, and a method wherein the free copper ion is sequestered by a sequestering agent. Examples of preferred sequestering agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid, hydroxyethylethylenediamine-triacetic acid, uramil diacetic acid, and metal salts (for example, sodium salt) of the above compounds.
When the free copper ion concentration falls within the above concentration range, precipitation after the production of the ink can be prevented. In addition, good storage stability, ejection stability, and clogging preventive effect can be attained.
The free copper ion concentration may be measured, for example, by ion chromatography, inductively coupled plasma mass spectroscopy (ICP-MS), or capillary electrophoresis.
When the copper complex colorant is a copper phthalocyanine pigment, the above free copper ion concentration is preferably realized by the addition of EDTA or a metal salt thereof. The amount of EDTA added may be properly determined so that precipitation can be suppressed. The content of EDTA is preferably not less than 20% by weight based on the copper phthalocyanine pigment. Since, however, the addition of EDTA in an excessive amount has a fear of the stability of the ink composition being deteriorated, the upper limit of the amount of EDTA added is preferably determined so that EDTA does not deteriorate the stability of the ink composition. Although the reason why the addition of EDTA can effectively prevent precipitation has not been fully elucidated yet, the reason is believed to reside in that the component derived from the copper phthalocyanine pigment is sequestered by EDTA. The present inventors have found that treating the copper phthalocyanine pigment with EDTA before the addition of the copper phthalocyanine pigment to the ink composition can provide an ink composition which is much less likely to cause precipitation. Thus, according to another aspect of the present invention, there is provided a process for producing an ink composition comprising a copper phthalocyanine pigment, said process comprising the steps of:
bringing a copper phthalocyanine pigment into contact with EDTA or a metal salt of EDTA; and
then producing an ink composition using the treated copper phthalocyanine pigment.
According to still another aspect of the present invention, there is provided an ink composition produced by this process.
According to a preferred embodiment of the present invention, in an ink composition comprising a copper complex dye and a benzotriazole compound as a rust preventive or a thiazole compound as antimold, the regulation of the free copper ion concentration can effectively prevent the occurrence of precipitate. According to experiments conducted by the present inventors, a combination of the benzotriazole compound as the rust preventive or the thiazole compound as the antimold with the copper complex dye has caused significant precipitation. The regulation of the free copper ion concentration, even when the ink composition contains the benzotriazole compound as the rust preventive or the thiazole compound as the antimold, can effectively prevent the occurrence of precipitate. The rust preventive and the antimold may also be, of course, added to ink compositions using copper phthalocyanine pigments as the copper complex colorant, and specific examples of preferred rust preventives and antimold will be described later.
According to a preferred embodiment of the present invention, the addition of EDTA to an ink composition comprising a copper phthalocyanine pigment, a penetrable solvent and/or a surfactant can effectively prevent precipitation. So far as the present inventors know, when the ink composition contains a copper phthalocyanine pigment and a penetrable solvent and/or a surfactant, the occurrence of precipitate is significant. The addition of EDTA can effectively prevent the precipitation even when the ink composition contains a copper phthalocyanine pigment and a penetrable solvent and/or a surfactant. The penetrable solvent and the surfactant may also be, of course, added to ink compositions using copper complex dyes as the copper complex colorant, and specific examples of preferred penetrable solvents and surfactants will be described later.
The ink composition according to the present invention preferably contains a rust preventive from the viewpoint of preventing corrosion of metallic portions which come into contact with the ink composition. Examples of preferred rust preventives include benzotriazoles, acid sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite. Among them, benzotriazoles are particularly preferred.
The ink composition according to the present invention preferably contains antimold. Mold grown by contamination with bacteria is often causative of deteriorated storage stability of the ink composition or nozzle clogging. The addition of the antimold can effectively prevent these unfavorable phenomena. Examples of preferred types of antimold include: thiazole and isothiazole compound, such as benzisothiazolone, isothiazolone, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-(thiocyanomethylthio)-benzothiazole, 2-mercaptobenzothiazole, and 3-allyloxy-1,2-benzisothiazole-1,1-oxide; sodium 2,2-dimethyl-6-acetoxydioxane-1,3-dihydroacetate, butyl p-hydroxybenzoate, potassium sorbate, sodium 2-pyridinethiol-1-oxide anionic surfactant, sodium benzoate, sodium propionate, and sodium dehydroacetate. Among them, thiazole and isothiazole compounds are particularly preferred. Proxel Series (Proxel BD, N, BD 20, GX, L, LV, XL-2, and TN), which are thiazole compounds available from ZENECA, may also be preferably utilized.
The ink composition according to the present invention preferably contains a penetrable solvent. Examples of penetrable solvents usable herein include alkyl ethers of polyhydric alcohols. Specific examples of alkyl ethers of polyhydric alcohols include ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether. They may be added alone or as a mixture of two or more.
The ink composition according to the present invention preferably contains a surfactant. Examples of surfactants usable herein include compounds represented by formula (I): 
wherein 0xe2x89xa6m+nxe2x89xa650; and R1, R2, R3, and R4 each independently represent an alkyl group (preferably a C1-6 alkyl group).
Commercially available products may be used as the compound represented by the formula (I). Specific examples thereof include OLFINE Y, OLFINE E 1010, Surfynol 82, Surfynol 440, Surfynol 465, and Surfynol 485 (all the above products being manufactured by Air Products and Chemicals Inc.). They may be added alone or in combination of two or more.
Examples of other surfactants usable herein include anionic surfactants (for example, sodium dodecylbenzenesulfonate, sodium laurylate, and an ammonium salt of polyoxyethylene alkyl ether sulfates), nonionic surfactants (for example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylenealkylamines, and polyoxyethylenealkylamides).
According to a preferred embodiment of the present invention, the copper phthalocyanine pigment is added, to the ink composition, as a pigment dispersion obtained by dispersing the pigment in an aqueous medium with the aid of a dispersant or a surfactant. Preferred dispersants include dispersants commonly used in the preparation of pigment dispersions, for example, polymeric dispersants. It would be apparent to a person having ordinary skill in the art that the dispersant and the surfactant contained in the pigment dispersion function also as the dispersant and the surfactant in the ink composition. Examples of preferred polymeric dispersants include naturally occurring polymeric compounds, and specific examples thereof include: proteins, such as glue, gelatin, casein, and albumin; naturally occurring rubbers, such as gum arabic and tragacanth; glucosides, such as saponin; alginic acid and alginic acid derivatives, such as propylene glycol alginate, triethanolamine alginate, and ammonium alginate; and cellulose derivatives, such as methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, and ethylhydroxycellulose. Examples of preferred polymeric dispersants include synthetic polymeric dispersants, and examples thereof include polyvinyl alcohols; polyvinyl pyrrolidones; acrylic resins, such as polyacrylic acid, acrylic acid/acrylonitrile copolymer, potassium acrylate/acrylonitrile copolymer, vinyl acetate/acrylic ester copolymer, and acrylic acid/acrylic ester copolymer; styrene/acrylic resins, such as styrene/acrylic acid copolymer, styrene/methacrylic acid copolymer, styrene/methacrylic acid/acrylic ester copolymer, styrene/xcex1-methylstyrene/acrylic acid copolymer, and styrene/xcex1-methylstyrene/acrylic acid/acrylic ester copolymer; styrene/maleic acid copolymer; styrene/maleic anhydride copolymer; vinylnaphthalene/acrylic acid copolymer; vinylnaphthalene/maleic acid copolymer; vinyl acetate copolymers, such as vinyl acetate/ethylene copolymer, vinyl acetate/fatty acid vinylethylene copolymer, vinyl acetate/maleic ester copolymer, vinyl acetate/crotonic acid copolymer, and vinyl acetate/acrylic acid copolymer; and salts of the above polymers. Among them, a copolymer of a monomer having a hydrophobic group with a monomer having a hydrophilic group and a polymer of a monomer having both a hydrophobic group and a hydrophilic group in its molecular structure are particularly preferred.
A preferred solvent usable in the ink composition according to the present invention comprises water and a water-soluble organic solvent. According to a preferred embodiment of the present invention, the ink composition of the present invention further comprises a wetting agent comprising a high-boiling organic solvent. Preferred examples of high-boiling organic solvents usable herein include polyhydric alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol, glycerin, trimethylolethane, and trimethylolpropane; urea; 2-pyrrolidone; N-methyl-2-pyrrolidone; and 1,3-dimethyl-2-imidazolidinone. The amount of the wetting agent added is preferably 2 to 30% by weight, more preferably 5 to 20% by weight, based on the ink composition.
The ink composition of the present invention may contain a saccharide. Examples of preferred saccharides usable herein include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), and other polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, aldonic acid, glucitol, sorbitol, maltose, cellobiose, lactose, sucrose, trehalose, and maltotriose. The term xe2x80x9cpolysaccharidexe2x80x9d used herein means saccharides in the broad sense as including substances which exist widely in the world of nature, such as alginic acid, xcex1-cyclodextrin, and cellulose. Derivatives of these saccharides usable herein include reducing sugars of the above saccharides (for example, sugar alcohols represented by the general formula HOCH2(CHOH)nCH2OH, wherein n is an integer of 2 to 5), oxidizing sugars (for example, aldonic acid or uronic acid), amino acids, and thiosugars. Among them, sugar alcohols are particularly preferred, and specific examples thereof include maltitol and sorbitol. The content of the saccharide is preferably about 1 to 10% by weight based on the ink composition.
If necessary, pH adjustors, rust preventives, preservatives, antimolds, phosphorus-based antioxidants and the like may be added to the ink composition of the present invention.
The ink composition may be prepared by dissolving or dispersing and mixing the above ingredients together by means of a suitable method. When the colorant is a copper phthalocyanine pigment, preferably, the pigment, the polymeric dispersant, and water are first mixed together by means of a suitable dispergator (for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a jet mill, or an angmill) to prepare a homogeneous pigment dispersion. Subsequently, water, EDTA, a penetrable solvent, a surfactant, a water-soluble organic solvent, a saccharide, a pH adjustor, a preservative, an antimold and the like are added to and satisfactorily dissolved in the pigment dispersion to prepare an ink solution. After thorough stirring, the ink solution is filtered to remove coarse particles and foreign matter causative of nozzle clogging to obtain a contemplated ink composition.